Application of negative corona discharge in the course of recording leads to an increase in the holographic sensitivity of the Cu–As2Se3 structure and diffraction efficiency of the recorded holographic gratings and the relief gratings fabricated with the aid of chemical etching. Positive corona discharge impedes the recording of holographic gratings in the Cu–As2Se3 structure. The Cu–As2Se3 structure exhibits the properties of a negative photoresist under irradiation in the presence of the negative corona discharge. In addition, the dissolution selectivity substantially increases due to the corona discharge.